WO2005110743A1 - Film d'emballage haute barrière ayant des matières extractibles reduites - Google Patents

Film d'emballage haute barrière ayant des matières extractibles reduites Download PDF

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Publication number
WO2005110743A1
WO2005110743A1 PCT/US2005/016411 US2005016411W WO2005110743A1 WO 2005110743 A1 WO2005110743 A1 WO 2005110743A1 US 2005016411 W US2005016411 W US 2005016411W WO 2005110743 A1 WO2005110743 A1 WO 2005110743A1
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Prior art keywords
pressure
low
density polyethylene
multilayered film
containing layer
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PCT/US2005/016411
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English (en)
Inventor
Carl E. Altman
David J. Gibboni
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Honeywell International Inc.
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Publication of WO2005110743A1 publication Critical patent/WO2005110743A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544—Addition polymer is perhalogenated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to multilayer films. More particularly, the invention pertains to coextruded or laminated barrier films having at least one layer of a fluoropolymer homopolymer or copolymer, a layer of a high-pressure, low-density polyethylene and an intermediate adhesive layer between said layers.
  • Such multilayer films substantially reduce or eliminate the extraction of contaminants from the barrier film into a packaged product.
  • thermoplastic polymers and films formed from thermoplastic polymers are known.
  • Important physical characteristics of such films include its barrier properties, including barriers to gas, aroma, and/or vapor such as water vapor, as well as its physical characteristics, such as toughness, wear and weathering resistances, and light-transmittance. These properties are especially important in film applications such as, for example, in the use of films as a packaging material for food or medical products.
  • a suitable means of reducing the cost of a packaging material fabricated from a costly polymer is to form multilayer structures in which the polymer film is laminated with other, less costly polymer films.
  • This approach is particularly desirable for the fluoropolymer packaging applications since a thin layer of the fluoropolymer is often all that is needed to take advantage of the desirable properties of the fluoropolymer while minimizing the cost.
  • fluoropolymers do not adhere strongly to most other polymers.
  • an adhesive tie layer may be used between adjacent layers.
  • U.S. patent 4,677,017 discloses coextruded multilayer films which include at least one fluoropolymer film and at least one thermoplastic film which are joined by the use of an adhesive polymer, particularly ethylene/vinyl acetate polymers, as an adhesive tie layer.
  • U.S. patent 4,659,625 discloses a fluoropolymer multilayer film structure which utilizes a vinyl acetate polymer adhesive tie layer.
  • patent 5,139,8708 discloses a fluoropolymer film structure using an adhesive tie layer of modified polyolefins.
  • U.S. patent 6,451,925 which is incorporated herein by reference, teaches a laminate of a fluoropolymer containing layer and a non-fluoropolymer containing layer using an adhesive tie layer which is a blend of an aliphatic polyamide and a fluorine-containing graft polymer.
  • U.S. patent 5,855,977 teaches applying an aliphatic di- or polyamine to one or more surfaces ofa fluoropolymer or non-fluoropolymer material layer.
  • Blister packaging is a packaging application that enables the consumer to see a product enclosed in clear plastic.
  • a clear or transparent plastic dome or bubble is preformed and attached to a paperboard (or other carrier) base, to encase the product.
  • the product is then typically forced out of the blister package by pushing it through the paperboard.
  • it is -desired to monoaxially orient the film in order to achieve one direction push through of the product.
  • a biaxially oriented film would be desired.
  • orientation of fluoropolymer films has been found to result in an even greater degree of moisture and vapor barrier properties above the standard fluoropolymer barrier properties.
  • U.S. patent 4,510,301 which is incorporated herein by reference, discloses oriented films containing a copolymer of 40 to 60 mole percent ethylene and chlorotrifluoroethylene.
  • U.S. patent 4,519,969 which is incorporated herein by reference, discloses a biaxially stretched film and a method for the manufacture thereof, containing at least 90 mole % of ethylene-tetrafluoroethylene copolymer.
  • U.S. patent 4,677,017 discloses coextruded multilayer films which include a fluoropolymer and a thermoplastic film which are joined by the use of an adhesive polymer.
  • patent 4,659,625 discloses a fluoropolymer multilayer film structure which utilizes a vinyl acetate polymer adhesive layer.
  • U.S. patent 5,139,878 discloses a fluoropolymer film structure using an adhesive layer of modified polyolefms.
  • multilayered fluoropolymer barrier films particularly those used for packaging of pharmaceuticals, food products or chemicals
  • additives or residual chemicals contained in the film layers can leach out of the film and into the packaged material. This contamination leads to the damage or destruction of the packaged product.
  • a multilayered packaging film structure that is leach resistant or minimizes the leaching or extraction of contaminants from the film into a packaged product is desired.
  • High-pressure, low- density polyethylenes are polyethylenes that are obtained by polymerizing ethylene at high temperatures under high pressures. They are described, for example, in U.S. patents 5,741,861 and 5,756,193, which are incorporated herein by reference. It has been found that the high-pressure, low-density polyethylene, when positioned as the innermost film layer which is in contact with the packaged product, will deter the leaching of contaminants from other film layers, protecting the product.
  • the invention provides a multilayered film which comprises at least one fluoropolymer containing layer and at least one high-pressure, low-density polyethylene containing layer attached to a surface of said fluoropolymer containing layer by an intermediate adhesive layer.
  • the invention further provides a method of producing a multilayered film which comprises laminating and attaching at least one fluoropolymer containing layer to a surface of at least one high-pressure, low-density polyethylene containing layer by an intermediate adhesive layer.
  • the invention still further provides articles and packages formed from the multilayered films of the invention, as well as packaged products contained in containers formed from the multilayered films of the invention.
  • the fluoropolymer containing layer has first and second surfaces and is joined with an adhesive tie layer such that the first surface of the fluoropolymer containing layer is in contact with a first surface of the adhesive tie layer.
  • Fluoropolymer materials are commonly known for their excellent chemical resistance and release properties as well as moisture and vapor barrier properties, and therefore are desirable components of packaging films.
  • the fluoropolymer containing layer may be comprised of fluoropolymer homopolymers or copolymers or blends thereof as are well known in the art and are described in, for example, U.S. patent numbers 4,510,301, 4,544,721 and 5,139,878 which are incorporated herein by reference.
  • Preferred fluoropolymers include, but are not limited to, homopolymers and copolymers of chlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, ethylene- tetrafluoroethylene copolymer, fluorinated ethylene-propylene copolymer, perfiuoroalkoxyethylene, polychlorotrifluoroethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, and copolymers and blends thereof.
  • copolymers include polymers having two or more monomer components.
  • the most preferred fluoropolymers include homopolymers and copolymers of poly(chlorotrifluoroethylene). Particularly preferred are PCTFE (polychlorotrifluoroethylene homopolymer) materials sold under the ACLON M trademark and which are commercially available from Honeywell International Inc. of Morristown, New Jersey.
  • Adjacent to the fluoropolymer containing layer is an adhesive layer, also referred to in the art as a "tie" layer, between each film layer.
  • a suitable adhesive tie layer as known in the art may be employed in accordance with the present invention.
  • adhesives include, but are not limited to, polyurethanes, epoxies, polyesters, acrylics, polyolefin plastomers, functionally modified polyolefins such as anhydride modified polyolefins and blends thereof.
  • Modified polyolefin compositions have at least one functional moiety selected from the group consisting of unsaturated polycarboxylic acids and anhydrides thereof.
  • Such unsaturated carboxylic acid and anhydrides include maleic acid and anhydride, fumaric acid and anhydride, crotonic acid and anhydride, citraconic acid and anhydride, itaconic acid an anhydride and the like. Of these, the most preferred is maleic anhydride. Also preferred are blends of polyolefin plastomers and functionally modified polyolefins.
  • the modified polyolefins suitable for use in this invention include compositions described in U.S. patents 3,481,910; 3,480,580; 4,612,155 and 4,751,270 which are incorporated herein by reference.
  • Other adhesive layers non-exclusively include alkyl ester copolymers of olef ⁇ ns and alkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as those described in U.S. patent 5,139,878.
  • the preferred modified polyolefin composition comprises from about 0.001 and about 20 weight percent of the functional moiety, based on the total weight of the modified polyolefin. More preferably the functional moiety comprises from about 0.05 and about 10 weight percent, and most preferably from about 0.1 and about 5 weight percent.
  • the modified polyolefin composition may also contain up to about 40 weight percent of thermoplastic elastomers and alkyl esters as described in U.S. patent 5,139,878.
  • the polymerized high-pressure, low-density polyethylenes of the- invention are polyethylene polymers having long-chain pendant branches, usually polymers whose pendant branches have at least about 20 carbon atoms.
  • the preferred high- pressure, low-density polyethylenes of the invention are further characterized by melting points in the range of from about 107°C to about 112°C, more preferably from about 108°C to about 111°C and most preferably from about 109 °C to about 110 °C.
  • the high-pressure, low- density polyethylenes preferably have a density of from about 0.910 g/cm 3 to about 0.925 g/cm 3 , more preferably from about 0.915 g/cm 3 to about 0.924 g/cm 3 and most preferably from about 0.919 g/cm to about 0.923 g/cm , according to the ASTM D-1505 testing method.
  • the high-pressure, low-density polyethylenes have a preferred melt flow index of from about 0.1 g/10 min. to about 12.0 g/10 min., more preferably from about 1 g/lOmin.
  • the high-pressure, low-density polyethylenes are formed at a processing temperature of from about 325°C to about 375°C, more preferably from about 335°C to about 365°C and most preferably from about 345°C to about 355°C.
  • high-pressure, low-density polyethylene layers of multilayered films of the invention are substantially devoid of contaminants capable of leaching out of the layer, and preferably contain no additives, such as, for example, heat stabilizers, aiitioxidants, secondary stabilizers, slip agents, antiblocking agents, UV Stabilizers and flame retardants. It is most preferred that each of the high-pressure, low- density polyethylene containing layer, fluoropolymer containing layer and intermediate adhesive layer are substantially devoid of such contaminants which are potentially capable of leaching out of said layers.
  • Preferred high-pressure, low-density polyethylenes may be obtained commercially, such as from Exxon-Mobil Chemical Company or Chevron Phillips Chemical Company. Preferred examples include Exxon-Mobil polyethylene grades LD 102.LN, LD 110.LN, LD 120.LN, LD 123.LN, LD 202.48 and LD 516.LN. Each of these are high-pressure, low-density polyethylenes formed from a high-pressure process and do not contain an added stabilizer composition.
  • the multilayer films of the present invention can have a variety of structures and preferably have an adhesive layer between each individual layer.
  • a typical film structure includes a three-layer structure, which comprises a high-pressure, low- density polyethylene containing layer, an adhesive layer and a fluoropolymer containing layer.
  • Another typical film structure is a five-layer structure, which comprises a high-pressure, low-density polyethylene containing layer, an adhesive layer, a fluoropolymer containing layer, an adhesive layer and a high-pressure, low-density polyethylene containing layer.
  • Optional additional layers may comprise a thermoplastic polymer layer such as a polyolefin, e.g. a polyethylene or polypropylene homopolymer or copolymer, a polyester, a polyolefin, a vinyl ester, polyamide, polyvinyl chloride, polyvinylidene chloride, poly(acrylonitrile) homopolymer or copolymer, polyvinyl alcohol or ethylene vinyl alcohol.
  • the polymeric layers of the invention may also be attached to one or more metal foil layers, such as an aluminum foil. Such films are well known in the art. Any additional layers may be added via well known lamination, coextrusion or coating techniques. It should be known, however, that should multilayered films be formed that have additional optional layers as discussed herein, the high-pressure, low-density polyethylene containing layer is preferably the innermost film layer of the barrier film, being in contact with the packaged product.
  • Each of the film layers may optionally also include one or more conventional additives whose uses are well known to those skilled in the art.
  • the use of such additives may be desirable in enhancing the processing of the individual layer compositions as well as improving the products or articles formed therefrom. However, it is most preferred that no additives are present in the high-pressure, low-density polyethylene containing layer.
  • oxidative and thermal stabilizers examples include: oxidative and thermal stabilizers, lubricants, release agents, flame-retarding agents, oxidation inhibitors, oxidation scavengers, dyes, pigments and other coloring agents, ultraviolet light absorbers and stabilizers, organic or inorganic fillers including particulate and fibrous fillers, reinforcing agents, nucleators, plasticizers, as well as other conventional additives known to the art.
  • all of the layers of the multilayered film are substantially devoid of such additives.
  • additives such may be used in amounts, for example, of up to about 10 % by weight of the overall layer composition.
  • Representative ultraviolet light stabilizers include various substituted resorcinols, salicylates, benzotriazole, benzophenones, and the like.
  • Suitable lubricants and release agents include stearic acid, stearyl alcohol, and stearamides.
  • Exemplary flame-retardants include organic halogenated compounds, including decabromodiphenyl ether and the like as well as inorganic compounds.
  • Suitable coloring agents including dyes and pigments include cadmium sulfide, cadmium selenide, titanium dioxide, phthalocyanines, ultramarine blue, nigrosine, carbon black and the like.
  • Representative oxidative and thermal stabilizers include the Period Table of Element's Group I metal halides, such as sodium halides, potassium halides, lithium halides; as well as cuprous halides; and further, chlorides, bromides, iodides. Also, hindered phenols, hydroquinones, aromatic amines as well as substituted members of those above mentioned groups and combinations thereof.
  • Exemplary plasticizers include lactams such as caprolactam and lauryl lactam, sulfonamides such as o,p- toluenesulfonamide and N-ethyl, N-butyl benylnesulfonamide, and combinations of any of the above, as well as other plasticizers known to the art.
  • the multilayer films of this invention may be produced by conventional methods useful in producing multilayer films, including coextrusion and lamination techniques that are well known in the art. Suitable coextrusion techniques are described in U.S. patents 5,139,878 and 4,677,017.
  • One advantage of coextruded films is the formation of a multilayer film in a one process step by combining molten layers of each of the film layers of fluoropolymer, tie layer composition, and high-pressure, low-density polyethylene containing layer, as well as optionally more film layers, into a unitary film structure.
  • compatible in this respect means that the film-forming compositions used to form the films have melt properties which are sufficiently similar so as to allow coextrusion.
  • Melt properties of interest include, for example, melting points, melt flow indices, apparent viscosity, as well as melt stability. It is important that such compatibility be present to assure the production of a multilayer film having good adhesion and relatively uniform thickness across the width of the film being produced.
  • film-forming compositions which are not sufficiently compatible to be useful in a coextrusion process frequently produce films having poor interfacial lamination, poor physical properties as well as poor appearance.
  • coextrusion process it is important that the constituents used to form the multilayer film be compatible within a relatively close temperature range in order to permit extrusion through a common die.
  • the coextruded film may be cast onto a casting roller or blown as a bubble which is then collapsed, using techniques well known in the art.
  • the multilayer films of the present invention can be produced by lamination whereby a multilayer film structure is formed from pre-fabricated film plies.
  • laminating is done by positioning the individual layers of the inventive film on one another under conditions of sufficient heat and pressure to cause the layers to combine into a unitary film.
  • the fluoropolymer, adhesive, and high-pressure, low-density polyethylene containing layers are positioned on one another, and the combination is passed through the nip of a pair of heated laminating rollers by techniques well known in the art such as those described in U.S. patent 3,355,347 which is incorporated herein by reference.
  • Lamination heating may be done at temperatures ranging from about 120°C to about 175°C, preferably from about 150°C to about 175°C at pressures ranging from about 5 psig (0.034 MPa) to about 100 psig (0.69 MPa) for from about 5 seconds to about 5 minutes, preferably from about 30 seconds to about 1 minute.
  • each layer of the multilayer film structure may have a different thickness
  • the thickness of each of the fluoropolymer and high-pressure, low-density polyethylene containing layers of the films in the post-stretched multilayer films structure is preferably from about 0.05 mils (1.3 ⁇ m) to about 100 mils (2540 ⁇ m), and more preferably from about 0.05 mils (1.3 ⁇ m) to about 50 mils (1270 ⁇ m).
  • the thickness of the post-stretched adhesive layer may vary, but is generally in the range of from about 0.02 mils to about 12 mils (305 ⁇ m), preferably from about 0.05 mils (1.3 ⁇ m) to about 1.0 mils (25 ⁇ m), and most preferably from about 0.1 mils (25 ⁇ m) to about 0.8 mils (20 ⁇ m). While such thicknesses are preferred as providing a readily flexible film, it is to be understood that other film thicknesses may be produced to satisfy a particular need and yet fall within the scope of the present invention; such thicknesses which are contemplated include plates, thick films, and sheets which are not readily flexible at room temperature (approx. 20°C).
  • the multilayered packaging films of the invention are superior to other known packaging films because they substantially reduce or entirely prevent the leachability of contaminants from the film into a packaged product.
  • the multilayered packaging films of the invention have been found to exhibit a leachability amount of less than about 1.0 parts per million (ppm), more preferably less than about 0.5 ppm and most preferably less than about 0.1 ppm of leachables as determined by conventional testing methods.
  • ppm parts per million
  • Another noteworthy characteristic of the films of the present invention is that they exhibit improved tensile modulus, mechanical strength, and the most significantly of all, excellent barrier properties towards both water vapor and oxygen after being stretched. With these composite films, the degree of attainable water vapor barrier properties is significantly improved without increasing the film gauge.
  • the multilayered films of the invention exhibit high sealability, exhibiting a seal strength of from about 0.5 lb/in to about 4 lb/in, more preferably from about 1 lb/in to about 4 lb/in and most preferably from about 1.5 lb/in to about 4 lb/in using a standard bar seal testing method.
  • the multilayered films of the invention also exhibit a haze percentage of preferably less than about 10%, more preferably less than about 5%.
  • the water vapor transmission rate (WVTR) of the films of the invention may be determined via the procedure set forth in ASTM F1249.
  • the overall multilayered film according to this invention has a WVTR of from about 0.1 or less gm/100 in 2 /day of the overall film at 37.8°C and 100% RH, preferably from 0.001 to about 0.07 gm/100 inVday of the overall film, and more preferably from 0.001 to about 0.04 gm/100 inVday of the overall film.
  • the oxygen transmission rate (OTR) of the films of the invention may be determined via the procedure of ASTM D-3985 using an OX-TRAN 2/20 instrument manufactured by Modem Controls, Inc., operated at 23°C, 0% RH.
  • the overall multilayered film according to this invention has an OTR of from about 50 or less cc/100 in 2 /day of the overall film preferably from about 0.001 to about 20 cc/100 in 2 /day of the overall film, and more preferably from about 0.001 to about 10 cc/100 in 2 /day of the overall film.
  • the multilayered films of the invention are particularly useful for forming thermoformed three dimensionally shaped articles such as rigid or soft blister packaging with peelable or push through lidding for pharmaceuticals or other products or materials. This may be done by forming the film around a suitable mold and heating in a method well-known in the art. The thermoformed film ma)' then be adjoined by coating, lamination or another suitable method with other films, foils or other materials to form a sealed or a sealable package.
  • the multilayered films of the invention are also particularly useful for forming transparent or opaque pouches, sachets and overwraps that may be formed, filled with a product and sealed. Examples of suitable products include, but are not limited to, liquids including water-based, alcohol-based and organic solvent-based solutions, assorted solid objects, powders, pharmaceuticals, nutraceuticals, devices such as sutures, catheters, test kits, etc.
  • a three-layer multilayered film was formed having a 2.0 mil thick layer of HL
  • Marlex® D350 grade polyethylene is produced with a stabilizer composition and not produced by the high pressure polymerization process according to the invention.
  • the polyethylene was processed in a 3.5" screw extruder using a standard polyethylene screw with five mixing zones heated to 430°F, 450°.F, 460°F, 460°F and 460°F respectively.
  • the Aclon® fluoropolymer was processed using a 2.0" screw against a casting roll with three mixing zones heated to 580°F, 540°F and 540°F respectively, and one adapter zone also set at 540°F.
  • the tie layer was processed using a 1.25" general screw extruder with three heating zones set at 120°F, 350°F and 500°F respectively, with an adapter zone set at.540°F. Three combining adapter zones were set at 460°F, 520°F and 520°F. Each of the dies were set at 520°F, the cast roll temperature was 65°F and the cool roll and heat set roll were each set at 100°F.
  • a multilayered film produced according to Example 1 is formed into a package and tested for leaching of stabilizer.
  • the package shows an unacceptable quantity of stabilizer contaminant that leaches out of the polyethylene.
  • Example 1 was repeated except the polyethylene layer was a 2.0 mil thick layer of LD 123 LN grade high-pressure, low density polyethylene, commercially available from Exxon Mobil Chemical Company.
  • a multilayered film produced according to Example 3 is formed into a package and tested for leaching of stabilizer.
  • the package shows no measurable stabilizer contaminant that leaches out of the polyethylene.

Landscapes

  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

Il est fourni des films multicouches co-extrudés ou stratifiés ayant au moins une couche d'un homopolymère ou d'un copolymère d'un fluoropolymère, une couche d'un polyéthylène basse densité obtenu sous haute pression et une couche d'attache adhésive intermédiaire. De tels films barrières réduisent en grande partie l'extraction de contaminants vers un produit emballé ou sont complètement résistants à une extraction.
PCT/US2005/016411 2004-05-11 2005-05-11 Film d'emballage haute barrière ayant des matières extractibles reduites WO2005110743A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/842,861 2004-05-11
US10/842,861 US20050252818A1 (en) 2004-05-11 2004-05-11 High barrier packaging film with controlled extractables

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WO2005110743A1 true WO2005110743A1 (fr) 2005-11-24

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* Cited by examiner, † Cited by third party
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GB0613135D0 (en) * 2006-06-30 2006-08-09 Glaxosmithkline Consumer Healt Toothbrush
CA2663929A1 (fr) * 2006-11-21 2008-05-29 Fina Technology, Inc. Polyethylene utilise pour produire des films et des article moules dans un procede qui fait appel a une tension en phase solide
EP2163379A4 (fr) * 2007-06-20 2012-06-13 Shionogi & Co Film stratifié en résine destiné à former une plaquette et plaquette
JP6990031B2 (ja) * 2017-03-17 2022-01-12 藤森工業株式会社 積層体、ブリスター容器、及びプレススルーパッケージ

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US5589028A (en) * 1994-11-03 1996-12-31 Elf Atochem North America, Inc. Bonding method employing tie layers for adhering polyethylene to fluoropolymers
WO1997048553A1 (fr) * 1996-06-20 1997-12-24 Alliedsignal Inc. Films de fluoropolymere a fort etirage
US5741861A (en) * 1992-12-03 1998-04-21 Mitsubishi Chemical Corporation Resin composition for laminates
JP2002275322A (ja) * 2001-03-19 2002-09-25 Ube Ind Ltd 射出成形用ポリエチレン組成物およびこの射出成形物

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JP3375780B2 (ja) * 1995-03-29 2003-02-10 三井化学株式会社 重包装袋用ポリエチレン樹脂組成物およびその組成物からなる重包装袋用ポリエチレン樹脂フィルム
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US5741861A (en) * 1992-12-03 1998-04-21 Mitsubishi Chemical Corporation Resin composition for laminates
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WO1997048553A1 (fr) * 1996-06-20 1997-12-24 Alliedsignal Inc. Films de fluoropolymere a fort etirage
JP2002275322A (ja) * 2001-03-19 2002-09-25 Ube Ind Ltd 射出成形用ポリエチレン組成物およびこの射出成形物

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